Apparatus for oligomerization in multiple stages with single fractionation column

ABSTRACT

In an oligomerization apparatus comprising at least two oligomerization reactors, at least portions of product streams from two reactors are separated in the same separator vessel; a liquid product stream from the first oligomerization reactor is fed to a fractionation column and a side cut from the fractionation column feeds the second oligomerization reactor.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a Division of prior application Ser. No. 11/014,049which was filed Dec. 16, 2004, now U.S. Pat. No. 7,803,978 the contentsof which are incorporated herein by reference thereto.

FIELD OF THE INVENTION

This invention relates to a process and apparatus for oligomerizinglight olefins to obtain gasoline range product. Specifically, the lightolefins are oligomerized in at least two stages with a commonfractionation column to separate product from unreacted olefins.

BACKGROUND OF THE INVENTION

Processes for the oligomerization of light olefins to produce C₈ olefinoligomers are known. Oligomerization processes have been long employedto produce high quality motor fuel from C₄ olefins. Such oligomerizationprocesses are also referred to as catalytic condensation andpolymerization with the resulting motor fuel often referred to aspolymer gasoline. Methods have always been sought to improve the octanenumber of the gasoline boiling range oligomerization products. Indirectalkylation is a noteworthy C₄ olefin dimerization process.

In one form of the indirect alkylation process, an ionic exchange resincatalyst oligomerizes light olefins to produce oligomers such as C₈olefins. In such processes, the oligomerization zone can be preceded bya dehydrogenation zone to convert paraffinic feed into olefinic feed ora dehydration zone to convert TBA to isobutylene and/or succeeded by ahydrogenation zone to convert heavy oligomeric olefins into heavyalkanes that can be blended with gasoline stock.

U.S. Pat. No. 4,313,016 discloses a heat exchanged oligomerizationreactor that contains a cationic exchange resin catalyst. C₄ olefinscontacted with the resin catalyst oligomerize to C₄ oligomers. Water ormethanol may be present in small amounts, insufficient to form anentrained second phase, to serve as a catalyst modifier.

Modern oligomerization processes often include an oxygenate such astert-butyl alcohol (TBA) and/or sec-butyl alcohol (SBA) in the feed formodifying the catalyst to maintain desired product selectivity. Themodifier does not participate in the reaction. References disclosingresin catalyzed oligomerization in the presence of an oxygenate modifierinclude U.S. Pat. No. 5,877,372 and EP 994 088 A1. TBA and SBA havebecome the resin catalyst modifier of preference.

In oligomerization processes, it is typically necessary to separateunreacted light olefins from the product heavy oligomers in the effluentfrom the oligomerization zone. Separation is conventionally performed ina distillation column typically following the oligomerization zone. Thelighter components comprising primarily unreacted C₄ ⁻ olefins andcompounds that were present in the feed stream exit from the overhead ofthe distillation column. The heavier components comprising C₅ ⁺ olefinsand primarily oligomers and compounds exit out the bottoms of thedistillation column. In U.S. Pat. No. 4,423,264; U.S. Pat. No. 6,011,191and WO 01/27053, the overhead stream is routed to a secondoligomerization reactor followed by a second separation. In U.S. Pat.No. 5,998,685, the overhead stream is recycled to the oligomerizationreactor.

An object of the present invention is to utilize at least two reactorsfor oligomerizing light olefins while sharing one product separationcolumn.

An additional object of the present invention is to take a side drawfrom the product separation column as feed to the second oligomerizationreactor.

SUMMARY OF THE INVENTION

We have discovered a process and apparatus for utilizing onefractionation column to separate product oligomers from light olefins ineffluent from more than one oligomerization reactor. More than oneoligomerization reactor may be necessary when high concentrations ofisobutylene are in the feed to manage the reaction exotherm due to thehigh heat of reaction of isobutylene oligomerization. We have discoveredthat a side cut from a common butene fractionation column may have theappropriate concentration of isobutylene to obtain sufficient conversionof isobutylene to diisobutene in a second oligomerization reactor. Theproduct from the second oligomerization reactor can then be directed tothe same butene fractionation column. The overhead stream from thefractionation column would not have sufficient concentration ofisobutylene, but too much isobutane to obtain sufficient conversion inthe second oligomerization reactor. Additionally, in an embodiment, aportion of the product from the first oligomerization reactor can berouted to a third oligomerization reactor and a portion of the productfrom the third oligomerization reactor fed to the same butenefractionation column to cut down on production of trimers and tetramers.Flash vessels can be used in an embodiment to make rough separations ofoligomerization reactor effluent between liquid and vapor to recycle thevapor containing unreacted feed to the reactor and send the liquidcontaining oligomeric product to the butene column for product recovery.

Additional objects, embodiments and details of this invention can beobtained from the following detailed description of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates a flow scheme of the present invention.

FIG. 2 illustrates a second embodiment of the flow scheme of FIG. 1.

DETAILED DESCRIPTION OF THE INVENTION

Oligomerization reaction feed is typically a C₄ cut from a debutanizingdistillation column that follows a fluid catalytic cracking (FCC) unit.This feed will typically comprise C₃ to C₅ aliphatic olefins. Greaterconcentrations of isobutylene in the feed produce more of the preferredhigh-octane gasoline product, diisobutene, also known as 2,2,4-trimethylpentene. High isobutylene feed is typically produced from thedehydrogenation of isobutane or the dehydration of tertiary butylalcohol (TBA). However, high concentrations of isobutylene in the feedraise the reaction temperature due to the high heat of reaction from thedimerization of isobutylene. Excessively high reaction temperatures maypromote side reactions and degrade product quality.

Catalyst used for butylene oligomerization reactions include protonicacids which generally have a Hammett acidity function of −4.0 or less.Examples of catalysts falling into this category include phosphoric acidcatalysts. Solid phosphoric acid catalyst has a Hammett acidity functionof approximately −5.0 or lower. A particularly preferred catalyst of thepresent invention is a sulfonic acid ion-exchange resin catalyst. Thisresin catalyst comprises sulfonic acid groups and may be prepared bypolymerizing or copolymerizing aromatic vinyl compounds followed bysulfonating. Examples of aromatic vinyl compounds include the following:styrene, vinyl toluene, vinyl naphthalene, vinyl ethylbenzene, methylstyrene, vinyl chlorobenzene and vinyl xylene. An acidic ion-exchangeresin contains typically approximately 1.3 to 2.0 sulfonic acid groupsper aromatic group. Preferred resins are those based on copolymers ofaromatic monovinyl compounds and aromatic polyvinyl compounds and inparticular divinyl compounds in which the concentration of polyvinylbenzene is approximately 1 to 20 wt-% of the copolymer. The particlesize of the ion-exchange resin is preferably approximately 0.15 to 1 mm.Furthermore, perfluorosulfonic acid resins consisting of copolymers ofsulphonylfluorovinyl ethyl and fluorocarbon compounds can be used.Various suitable ion-exchange resins are commercially available underthe name, for example, AMBERLYST 15 and AMBERLYST 36. The concentrationof the catalyst is typically 0.01 to 20% of the mixture it is catalyzingand preferably 0.1 to 10% of the weight thereof.

A non-reactive, water-soluble oxygenate modifier such as an alcohol withat least three carbons and preferably TBA and/or SBA is also added tothe oligomerization reactor to attenuate the resin catalyst but not toparticipate in the reaction. TBA is also generated in the reaction zonewhen isobutene reacts with water over a resin catalyst. Similarly, SBAis generated from a reaction of water and normal butene. Additionally,other alcohols will form if other olefins, such as C₃ and C₅ olefins,are in the feed when they encounter water in the presence of the resincatalyst. Moreover, olefins and the alcohol modifier react over resincatalyst to generate ethers. The concentration of oxygenate modifieradded to the fresh feed will be 1 to 4 wt-%.

Oligomerization reaction zones in general are maintained at conditionsthat may vary widely. The temperature of the oligomerization reactionzones of the present invention in which a resin catalyst is used istypically about 50° to about 250° C. and preferably about 50° to about150° C. Pressures in the oligomerization zone using the resin catalystwill be sufficient to maintain the liquid phase in and out of thereactor, typically about 345 to about 3447 kPa (50 to 500 psig), andpreferably about 1380 to about 2413 kPa (200 to 350 psig).Oligomerization conditions may also include a liquid hourly spacevelocity (LHSV) of about 0.5 to about 8 hr⁻¹ with about 1 to about 6hr⁻¹ being preferred. In an embodiment, at least a portion of theoligomerization reactor product effluent may be directly recycled to thereactor inlet without undergoing a prior product separation. Directproduct recycle provides greater water solubility which facilitatescatalyst attenuation by the oxygenate modifier as well as exothermictemperature control.

A butene distillation fractionation column of the present inventionusually runs at pressures of between about 413 and about 1034 kPa (60and 150 psig) and preferably between about 483 and about 621 kPa (gauge)(70 and 90 psig) at the receiver. To make the separation between C₄ andC₈ hydrocarbons at those pressures, the bottoms temperature will have tobe between about 149° and about 232° C. (300° to 450° F.) and preferablybetween about 191° to about 204° C. (375° to 400° F.) and the overheadtemperature will have to be between about 38° to about 66° C. (100° to150° F.) and preferably between about 41° to about 52° C. (105° to 125°F.) at the receiver to obtain the appropriate separation.

Any suitable reflux ratio can be employed in the distillation column.The reflux ratio in the overhead is the weight ratio of the portion ofcondensed vapor which is returned to the distillation column to theportion of condensed vapor which is withdrawn as distillate product.Generally, the reflux ratio is in the range of from about 0.5:1 to about1.5:1. The reboil ratio in the bottoms is the weight ratio of theportion of vaporized liquid which is returned to the distillation columnto the portion of liquid which is withdrawn as bottoms product.Generally, the reboil ratio is in the range of from about 3:1 to about5:1.

The invention is disclosed with reference to FIGS. 1 and 2 which showoligomerization flow schemes which use a resin catalyst in theoligomerization reactors. However, other oligomerization reactionprocesses can be used in accordance with the present invention. Theoligomerization reactors preferably contain the same catalyst.

Feed comprising a C₄ hydrocarbon stream with preferably at least 40 wt-%isobutylene is brought into the process via a feed line 10. A modifierstream comprising an oxygenate such as an alcohol and preferablytert-butyl alcohol (TBA) and/or sec-butyl alcohol (SBA) in an azeotropicmixture with water are added to the feed line 10 via a modifier line 12.The alcohol and water in the modifier line 12, a portion of reactorrecycle in a line 16 and condensed reactor vapor stream in a line 18 arecombined with the feed in the first feed line 10 to form a combined feedline 20. The combined feed line 20 is heated by a heater 22 and enters afirst oligomerization reactor 24 through a first feed inlet. In anembodiment, the first reactor 24 operates in down flow mode, but up flowmay be suitable. Alternatively, several of the feed lines 10, 12, 16 or18 may enter the oligomerization reactor 24 separately. In theoligomerization reactor 24, the feed contacts a solid acid catalyst,preferably a resin catalyst under oligomerization conditions. The lightolefins in the feed which are preferably predominantly C₄ olefins andparticularly isobutylene oligomerize to heavy oligomers which arepreferably predominantly C₈ olefins and particularly diisobutene. Theconversion in the first reactor is typically about 50 to about 80 wt-%on a fresh feed basis. The conversion can be maintained at a moderatelevel without producing heavier oligomers because a subsequent reactorwill make up the conversion. The oligomerization effluent comprisingunreacted light olefins, product oligomers, alcohol modifier and waterexits the first reactor 24 in a first product stream through a firstproduct outlet carried via a first product line 26. A first portion ofthe oligomerization effluent is directly recycled to the first reactor24 without undergoing separation via the line 16 and a second portion ofthe oligomerization effluent in a line 28 is heated in a heater 30 andflashed in a first flash vessel 32. Vapor from the first flash vessel 32exits a flash vapor outlet in a flash vapor line 34 comprisingpredominantly light unoligomerized olefins and alkanes is condensed in acondenser 36 and split between the first line 18 carrying the condensedreactor vapor stream and a second line 38. The first flash vessel 32 ispreferably a rectifier with flashing occurring in the upper open portionof the vessel above a first tray and further fractionation occurring inone or more trays in a lower portion of the vessel 32. Two trays arepreferred. The preferred temperature ranges in the two-stage rectifierfirst flash vessel 32 is between about 71° and about 82° C. (160° to180° F.) in the overhead and between about 88° to about 99° C. (190° to210° F.) in the bottoms. The preferred pressure in the overhead of therectifier first flash vessel 32 is between about 620 to about 758 kPa(gauge) (90 to 110 psig). The condenser 36 may preferably refluxcondensed vapor back to the upper open portion of the vessel. Liquidbottoms exits the flash liquid outlet from the first flash vessel 32comprising predominantly oligomerized product and modifier and iscarried to a butene column 46 in a first product column feed line 40.

The butene column operates in a temperature and pressure rangesufficient to take the predominant majority of C₄ hydrocarbons in theoverhead and the predominant majority of C₈ hydrocarbons, typicallydiisobutene in the bottoms as previously stated. The overhead product ina line 48 is condensed in a condenser 50 and a portion is returned tothe column 46 while an overhead product is recovered in a line 52. Theoverhead product in the line 52 will predominantly contain light olefinsand alkanes a part or all of which may be recycled to the line 10 ortransported to an upstream dehydrogenation unit or to a downstreamalkylation unit. The bottoms product will predominantly containoligomers, ethers and a majority of TBA and/or SBA modifier. The bottomsproduct in a line 56 is vaporized in a reboiler 58 and a portionreturned to the column 46 while an oligomeric product is recovered in aline 60. The olefinic oligomeric product may be taken to a downstreamsaturator to yield saturated gasoline product. Optionally, the oxygenatemodifier may be water washed from the olefinic oligomeric product.

A side cut taken from a side cut outlet from the butene column 46 abovethe feed inlet for the line 40 is transported in a second feed line 62and combined with the condensed vapor stream in the line 38 and a secondreactor recycle in a line 64. The side cut is preferably a liquid draw.However, if the side cut is a vapor draw, a compressor or pump may benecessary to transport the vapor in the line 62. The combined feed iscarried in a line 66 and heated in a preheater 68 before entering asecond oligomerization reactor 70 through a second reactor inlet. In anembodiment, the second reactor 70 operates in down flow mode, but upflow may be suitable. Alternatively, several of the feed lines 62, 64,or 38 may enter the second oligomerization reactor 70 separately. In theoligomerization reactor 70, the feed contacts a solid acid catalyst,preferably a resin catalyst under oligomerization conditions. The lightolefins in the feed which are preferably predominantly C₄ olefins andparticularly isobutylene oligomerize to heavy oligomers which arepreferably predominantly C₈ olefins and particularly diisobutene. Theconversion in the second reactor is typically about 40 to about 60 wt-%on a fresh feed basis which is less than in the first reactor 24 becauseless isobutylene is in the feed to the second feed line 62 to the secondreactor 70 than in first feed line 10. The oligomerization effluentcomprising unreacted light olefins, product oligomers, alcohol modifierand water is carried via a second product outlet line 72 and split. Afirst portion of the oligomerization effluent is directly recycled tothe second reactor 70 without undergoing separation via the line 64 anda second portion of the oligomerization effluent in a line 74 is heatedin a heater 76 and enters a second flash inlet to be flashed in a secondflash vessel 78. The preferred temperature range in the second flashvessel 78 is between about 66° and about 71° C. (150° to 160° F.). Thepreferred pressure in the second flash vessel 78 is between about 758 toabout 896 kPa (gauge) (110 to 130 psig). It is contemplated that thesecond flash vessel could be a multi-stage rectifier. Vapor from thesecond flash vessel 78 exits a vapor outlet in a vapor return line 80and is condensed in a cooler 82 and fed to the butene column 46. Liquidexits from the flash vessel 78 through second flash exit and istransported in a liquid return line 84 and fed to the butene column 46.

Isobutane boils at a lower temperature than isobutene at the pressuresin the butene column 46. Hence, the feed and side cut points must bedistributed accordingly. The first product column feed line 40 carryingliquid product from the first flash vessel 32 will have the greatestconcentration of diisobutene product of the feeds to the column 46.Hence, a feed point 40 a for the line 40 should be in the lower half ofthe column 46 and preferably the lower quarter of the column 46 becauseproduct oligomers are recovered in the bottoms product in the line 60.The second flash liquid return line 84 carrying liquid product from thesecond flash vessel 78 will have the second greatest concentration ofdiisobutene product of the feeds to the column 46. Hence, a feed point84 a for the line 84 should also be in the lower half and preferably thelower quarter of the column 46 but above the feed point 40 a. The feedwithdrawn from the column 46 in the second reactor feed line 62 for thesecond reactor 70 should have an adequate concentration of isobutyleneto obtain adequate conversion in the second reactor 70. Hence, awithdrawal point 62 a for the line 62 should be above the bottom quarterand preferably below the top quarter of the column 46 and above the feedpoints 40 a and 84 a. The second flash vapor return line 80 carryingcondensed flash vapor from the second flash vessel 78 will have thegreatest concentration of isobutene of the feeds to the column 46.Hence, a feed point 80 a for the line 80 should be in the top half ofthe column, but preferably below the top quarter and above thewithdrawal point 62 a and the feed points 40 a and 84 a.

If the isobutylene concentration in the fresh feed approaches 50 wt-%,preferably above 45 wt-%, an embodiment of the present invention with athird reactor shown in FIG. 2 may help maintain production ofundesirable butene trimers and tetramers at an acceptable level. FIG. 2uses the same reference numerals for elements that are the same inFIG. 1. For elements in FIG. 2 that are changed from the correspondingelement in FIG. 1, the reference numeral will be marked with a primesymbol (′).

A portion of the condensed vapor from the first flash vessel 32 iscarried in a third feed line 38′ to a third oligomerization reactorsystem. Condensed vapor in a line 100 and third oligomerization reactorrecycle in a line 102 are mixed with the condensed vapor in the line38′. The combined feed in a line 104 is heated by a heater 106 andenters a third oligomerization reactor 108 through a third reactorinlet. In an embodiment, the third reactor 108 operates in down flowmode, but up flow may be suitable. Alternatively, several of the feedlines 38′, 100 and 102 may enter the third oligomerization reactor 108separately. In the third oligomerization reactor 108, the feed contactsa solid acid catalyst, preferably a resin catalyst under oligomerizationconditions. The light olefins in the feed which are preferablypredominantly C₄ olefins and particularly isobutylene oligomerize toproduct oligomers which are preferably predominantly C₈ olefins andparticularly diisobutene. The conversion in the third reactor istypically about 10 to about 20 wt-% on a fresh feed basis. Theisobutylene conversion in the third reactor 108 is greater than in thesecond reactor 70 and less than in the first reactor 24 because theisobutylene concentration in the third feed line 38′ is greater thanthat in the second feed line 62 fed to the second reactor 70 and lessthan in the first feed line 10 fed to the first reactor 24. The thirdoligomerization reactor effluent comprising unreacted light olefins,product oligomers, alcohol modifier and water exits the third reactoroutlet and is carried via a third product line 110. A first portion ofthe third oligomerization reactor effluent is directly recycled to thethird reactor 108 without first undergoing separation via the line 102and a second portion of the oligomerization effluent in a line 112 isheated in a heater 114 and enters through a third flash inlet to beflashed in a third flash vessel 116. Vapor from the third flash vesselexiting a third vapor outlet in a third vapor line 118 comprisingpredominantly light unoligomerized olefins and alkanes is condensed in acondenser 120 and split between the first line 100 carrying thecondensed reactor vapor stream for recycle to the third oligomerizationreactor 108 via the line 104 and a second line 122. The second line 122carries the condensed reactor vapor stream to be combined with thebutene column side cut stream in the second reactor feed line 62 and thesecond reactor recycle stream in the line 64. As stated with respect toFIG. 1, the combined feed in the line 66 is heated and delivered to thesecond oligomerization reactor 70. The third flash vessel 116 ispreferably a two-stage rectifier with flashing occurring in the upperopen portion of the vessel and further fractionation occurring in one ormore trays in a lower portion of the vessel 116. Two trays arepreferred. The preferred temperature ranges in the rectifier third flashvessel 116 is between about 57° and about 68° C. (135° to 155° F.) inthe overhead and between about 68° to about 77° C. (155° to 170° F.) inthe bottoms. The preferred pressure in the overhead of the two-stagerectifier third flash vessel 116 is between about 620 to about 758 kPa(gauge) (90 to 110 psig). The condensed vapor from the condenser 120 inthe line 118 may preferably be refluxed back to the upper open portionof the vessel. Liquid bottoms exits flash liquid outlet from the thirdflash vessel 116, comprising predominantly oligomerized product andmodifier, and is carried by a third flash liquid line 124 to join a line40′ carrying liquid bottoms from the first flash vessel 32. The combinedliquid product is carried to the butene column 46 by a line 126. A feedpoint 126 a for the line 126 to the butene column should be placed inthe same relative location as for the feed point 40 a with respect toFIG. 1.

Example I

We simulated a process using the flow scheme of FIG. 1. The feedcomposition is a 50 wt-% isobutene and 50 wt-% isobutane with anadequate amount of oxygenate modifier added. The feed rate is 45,359kg/hr (100,000 lb/hr) to the reactor. The butene column has 37 stages.The flow scheme of FIG. 1 is simulated to operate as shown in Table I.

TABLE I First Second Reactor Reactor Overall Isobutylene Conversion,wt-% Basis Fresh Feed 78.3 19.7 98.0 Per Pass 44.7 50.6 n.a. IsobutyleneConcentration in 25.0 4.3 n.a. Combined Feed, wt-% Ratio of Side Draw toFresh 2.6 Feed

The overall isobutylene conversion of 98 wt-% on a fresh feed basis isacceptable with feasible per pass conversions in each of the tworeactors.

Example II

We simulated a process using the flow scheme of FIG. 2. The feedcomposition, column stages and flow rates are the same as in Example I.The flow scheme of FIG. 2 was simulated to operate as shown in Table II.

TABLE II First Second Third Reactor Reactor Reactor Overall IsobutyleneConversion, wt-% Basis Fresh Feed 78.3 8.4 11.3 98.0 Per Pass 44.7 50.266.7 Isobutylene Concentration in 25.0 3.4 8.6 n.a. Combined Feed, wt-%Ratio of Side Draw to Fresh 1.5 Feed

The overall isobutylene conversion of 98 wt-% on a fresh feed basis isstill acceptable with feasible per pass conversions in each of the threereactors. However, the rate of feed withdrawn from the butene column isrelatively less than in Example I because less isobutylene conversion isrequired in the second reactor to obtain the same overall conversion.Additionally, in the flow scheme of Example II, overall trimer andtetramer production is kept below 10 wt-% on a fresh feed basis.

1. An apparatus for oligomerizing light olefins and recovering productoligomers comprising: a first oligomerization reactor vessel including afeed inlet for delivering light olefins to the reactor vessel and afirst product outlet for removing light olefins and product oligomersfrom said first oligomerization reactor vessel; a first product linewith a first end in fluid communication with said first product outletof said first oligomerization reactor vessel and a second end incommunication with a fractionation column; a feed line with a first endin fluid communication with a side cut outlet of said fractionationcolumn and a second end in fluid communication with an inlet to a secondoligomerization reactor vessel; a second product outlet for removinglight olefins and product oligomers from said second oligomerizationreactor vessel; and a return line with a first end in fluidcommunication with said second product outlet and a second end in fluidcommunication with said fractionation column.
 2. The apparatus of claim1 further including a flash vessel in fluid communication with saidfirst product outlet, said flash vessel having a liquid outlet in fluidcommunication with said fractionation column.
 3. The apparatus of claim1 wherein said first end of said feed line is connective with a side cutoutlet of said fractionation column.